US4163646A - Fuel oils containing N,N-substituted diamines - Google Patents
Fuel oils containing N,N-substituted diamines Download PDFInfo
- Publication number
- US4163646A US4163646A US05/755,535 US75553576A US4163646A US 4163646 A US4163646 A US 4163646A US 75553576 A US75553576 A US 75553576A US 4163646 A US4163646 A US 4163646A
- Authority
- US
- United States
- Prior art keywords
- sub
- alkyl
- compound
- group
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000295 fuel oil Substances 0.000 title claims description 27
- 150000004985 diamines Chemical class 0.000 title abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims 5
- 230000000087 stabilizing effect Effects 0.000 claims 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- -1 2,4-diamino-2-substituted pentanes Chemical class 0.000 abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 239000002816 fuel additive Substances 0.000 abstract description 4
- 150000002466 imines Chemical class 0.000 abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 2
- 150000005326 tetrahydropyrimidines Chemical class 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 239000000446 fuel Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000654 additive Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- UBDACAVHRSYUMJ-UHFFFAOYSA-N 2-methyl-4-n-(2-methylpropyl)pentane-2,4-diamine Chemical compound CC(C)CNC(C)CC(C)(C)N UBDACAVHRSYUMJ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000003292 diminished effect Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 150000001728 carbonyl compounds Chemical class 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000010771 distillate fuel oil Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000006078 metal deactivator Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 3
- ZKRSEUBKYMIMQG-UHFFFAOYSA-N 2-n-cyclohexyl-2-methylpentane-2,4-diamine Chemical compound CC(N)CC(C)(C)NC1CCCCC1 ZKRSEUBKYMIMQG-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 2
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 description 2
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 description 2
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 208000002430 Multiple chemical sensitivity Diseases 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- XHCADAYNFIFUHF-TVKJYDDYSA-N esculin Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=C1)O)=CC2=C1OC(=O)C=C2 XHCADAYNFIFUHF-TVKJYDDYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NSSSNQWFCWHZLY-UHFFFAOYSA-N (2-pentylphenyl) 2-methylprop-2-enoate Chemical compound CCCCCC1=CC=CC=C1OC(=O)C(C)=C NSSSNQWFCWHZLY-UHFFFAOYSA-N 0.000 description 1
- OHFXUPDPPRJZES-UHFFFAOYSA-N 1,2,5,6-tetrahydropyrimidine Chemical class C1CC=NCN1 OHFXUPDPPRJZES-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NUGOTBXFVWXVTE-UHFFFAOYSA-N 2-hydroxy-3-nitrobenzaldehyde Chemical compound OC1=C(C=O)C=CC=C1[N+]([O-])=O NUGOTBXFVWXVTE-UHFFFAOYSA-N 0.000 description 1
- PCXAQLMRLMZKRL-UHFFFAOYSA-N 2-methylpentane-2,4-diamine Chemical class CC(N)CC(C)(C)N PCXAQLMRLMZKRL-UHFFFAOYSA-N 0.000 description 1
- CUOYGVNOMILKIC-UHFFFAOYSA-N 2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O CUOYGVNOMILKIC-UHFFFAOYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- ZEZNTASFXDNPHK-UHFFFAOYSA-N 3-formyl-2-hydroxybenzonitrile Chemical compound OC1=C(C=O)C=CC=C1C#N ZEZNTASFXDNPHK-UHFFFAOYSA-N 0.000 description 1
- YOEUNKPREOJHBW-UHFFFAOYSA-N 3-formylsalicylic acid Chemical compound OC(=O)C1=CC=CC(C=O)=C1O YOEUNKPREOJHBW-UHFFFAOYSA-N 0.000 description 1
- UJHVKLMYJAONMU-UHFFFAOYSA-N 4,4,6-trimethyl-2,3-dihydro-1h-pyrimidine Chemical compound CC1=CC(C)(C)NCN1 UJHVKLMYJAONMU-UHFFFAOYSA-N 0.000 description 1
- FUGKCSRLAQKUHG-UHFFFAOYSA-N 5-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Cl)C=C1C=O FUGKCSRLAQKUHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 101710190405 Chalcone synthase B Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GQWNECFJGBQMBO-UHFFFAOYSA-N Molindone hydrochloride Chemical compound Cl.O=C1C=2C(CC)=C(C)NC=2CCC1CN1CCOCC1 GQWNECFJGBQMBO-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 150000003946 cyclohexylamines Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/74—Quinazolines; Hydrogenated quinazolines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
Definitions
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which may be the same or different, are hydrogen or substituted group such as alkyl, aryl, cycloalkyl, alkaryl, aralkyl, heterocyclic, substituted derivatives thereof, etc.
- R groups may be joined in a cyclic configuration which makes the THP structure a part of the substituted group.
- Alkyl includes methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, escosyl, docosyl, etc., for example having about 1-25 or more carbons such as from about 1-18 carbons, but preferably about 1-12 carbons.
- alkyl also includes isomers of the straight chain where branching occurs.
- Cycloalkyl includes cyclopentyl, cyclohexyl, etc., and derivatives thereof such as alkyl-cyclohexyl, dialkylcyclohexyl, etc.
- Aryl, alkaryl and aralkyl including phenyl, alkylphenyl, polyalkylphenyl, chlorophenyl, alkoxyphenyl, naphthyl, alkylnaphthyl, etc., benzyl, substituted benzyl, etc.
- the joining of the R groups into a ring structure include those structures derived from reactants of the general formula ##STR2## such as cyclohexanone, cyclopentanone, substituted derivatives thereof such as alkyl-cyclohexanone, dialkyl-cyclohexanone.
- 2,2-di-substituted derivatives of Formula I can be converted to linear diamines such as N-substituted-2,4-diamino-2-substituted pentanes by hydrogenation.
- a compound of Formula II can be converted to an amine-imine by reacting with a carbonyl compound.
- the methyl groups may be replaced with other groups such as for example hydrogen, higher alkyls, aryls, cycloalkyls, etc.
- the hydrogenation reaction is carried out in the presence of a hydrogenation catalyst such as palladium, platinum, nickel, etc.; at a suitable temperature, for example from ambient to 200° C. or higher, but preferably 50°-150° C.; at pressures sufficient to contain hydrogen in the reaction vessel, such as about 10-2000 psi, or higher but preferably about 200-1000 psi; for a sufficient period of time for the reaction to take place such as from about 10 minutes to 24 hrs. or longer, preferably from about 1/2 hr. to 6 hrs.; in solvents which do not interfere with the catalyst, reactants, or products such as water, alcohol, hydrocarbons, esters, etc.
- a hydrogenation catalyst such as palladium, platinum, nickel, etc.
- the preparation of the imine compound is conventional.
- the reaction can be carried out by heating the amine with substantially stoichiometric amounts of the carbonyl compound under dehydrating conditions, i.e., 1:1 molar ratio, for example by the use of an azeotroping agent.
- the imine compound resulting from the carbonyl reaction can be further reduced in the manner of Step 1 to yield the substituted diamine.
- R 7 and R 8 which may be the same or different, are hydrogen or substituted group such as alkyl, aryl, cycloalkyl, alkaryl, aralkyl, heterocyclic, substituted derivatives thereof, etc.
- R groups may be joined in a cyclic configuration.
- Alkyl includes methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, escosyl, docosyl, etc., for example having about 1-25 or more carbons such as from about 1-18 carbons, but preferably about 1-12 carbons.
- alkyl also includes isomers of the straight chain where branching occurs.
- Cycloalkyl includes cyclopentyl, cyclohexyl, etc., and derivatives thereof such as alkyl-cyclohexyl, dialkylcyclohexyl, etc.
- Aryl, alkaryl and aralkyl include phenyl, alkylphenyl, polyalkylphenyl, chlorophenyl, alkoxyphenyl, naphthyl, alkylnaphthyl, etc., benzyl, substituted benzyl, etc.
- the joining of the R groups into a ring structure include those structures derived from reactants of the general formula ##STR6## such as cyclohexanone, cyclopentanone, substituted derivatives thereof such as alkyl-cyclohexanone, dialkyl-cyclohexanone.
- fuel oils have a tendency to deteriorate in storage and form soluble colored bodies and insoluble sludge therein.
- This deterioration of the oil is highly undesirable in that it causes serious adverse effects on the characteristics of the oil, particularly on the ignition and burning qualities thereof. It is also a contributory factor, along with the presence of other impurities in the oil, such as rust, dirt and moisture, in causing clogging of the equipment parts, such as screens, filters, nozzles, etc., as is explained further herein.
- An important economical factor is also involved in the problem of oil deterioration in storage, viz., customer resistance. Thus, customers judge the quality of an oil by its color and they oftentimes refuse to purchase highly colored oils. It will be appreciated then that since fuel oils of necessity are generally subject to considerable periods of storage prior to use, the provision of a practical means for preventing the deterioration of the fuel oil during storage would be a highly desirable and important contribution to the art.
- the amount of additive employed will vary depending on various factors, for example the particular oil to be stabilized, the conditions of storage, etc.
- the stability of an oil depends largely on the nature of the crude oil from which it is made, the type of processing involved during refining, etc., and therefore some oils will require more additive to stabilize them than others.
- caustic-treated oil will, in general, require less additive than untreated oil of similar character.
- Fuel oils in general are contemplated by the invention.
- the fuel oils with which this invention is especially concerned are hydrocarbon fractions having an initial boiling point of at least about 100° F. and an end point not higher than about 750° F., and boiling substantially continuously throughout their distillation range.
- Such fuel oils are generally known as distillate fuel oils. It will be understood, however, that this term is not restricted to straight-run distillate fractions.
- the distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillates, naphthas and the like, with cracked distillate stocks.
- such fuel oils can be treated in accordance with well known commercial methods, such as acid or caustic treatment, solvent refining, clay treatment, etc.
- distillate fuel oils are characterized by their relatively low viscosities, low pour points, and the like.
- the principal property which characterizes the contemplated hydrocarbon fractions, however, is the distillation range. As mentioned herein, this range will lie between about 100° F. and about 750° F. Obviously, the distillation range of each individual fuel oil will cover a narrower range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
- Nos. 1, 2 and 3 fuel oils used in domestic heating and as diesel fuel oils particularly those made up chiefly or entirely of cracked distillate stocks.
- the domestic heating oils generally conform to the specifications set forth in A.S.T.M. Specifications D396-48T.
- Specifications for diesel fuels are defined in A.S.T.M. Specifications D975-48T.
- fuels for jet combustion engines are also contemplated herein. Typical jet fuels are defined in Military Specification MIL-F-5624B.
- diesel fuel test is a standard test for diesel fuel stability and is regarded as a rapid screening test for discovering new systems, which can be used to stabilize petroleum distillate fuels.
- the test involves exposing 50 ml. samples of fuel, containing desired quantities of fuel additives, to the test where a bath is held at 300° F. and the samples are exposed for 90 minutes.
- the exposed fuel is passed through a moderately retentive filter paper and the degree of stain on the filter paper noted.
- additives of this invention are useful as fuel additives per se their performance may be enhanced by employing certain auxiliary chemical aids.
- chemical aids are dispersants, for example acrylic polymers or copolymers which can be employed in conjunction with the cyclohexylamines.
- auxiliary chemical component is the copolymer derived from an acrylic ester of the formula: ##STR11## and N-vinyl-2-pyrrolidone, for example a copolymer containing the following units: ##STR12## having a molecular weight for example of at least 50,000, for example 50,000-500,000, or higher, but preferably 100,000-400,000 with an optimum of 300,000-400,000 of which vinyl pyrrolidone comprises at least 1% by weight, of the polymer, for example 1-30%, but preferably 3-15% with an optimum of 5-10%; where Y is hydrogen, a lower alkyl group such as methyl, ethyl, etc., Z is an hydrocarbon group having, for example, 1-30 carbon atoms, but preferably 8 to 18 carbon atoms.
- polymers are preferably acrylic or methacrylic polymers, or polymers derived from both in conjunction with vinyl pyrrolidone.
- the Z group on the polymer which can be the same throughout or mixed, can be octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, etc.
- Lower alkyl groups can also be employed such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc., but they preferably are employed as copolymers of the higher Z groups, for example a copolymer of dodecyl methacrylate and methyl acrylate, etc.
- the acrylic ester units may be derived from one or more acrylic type monomers and may be fully acrylic or fully methacrylic or both acrylic and methacrylic.
- the polymer may be random, block, graft, etc.
- Z may also be an alkylated aromatic group such as butyl phenyl, amyl phenyl, etc., or a cycloaliphatic group such as cyclohexyl.
- suitable monomeric esters are: methyl acrylate, ethyl acrylate, propyl methacrylate, amyl acrylate, lauryl acrylate, cetyl acrylate, octadecyl acrylate, amyl methacrylate, lauryl methacrylate, cetyl methacrylate, octadecyl methacrylate, amylphenyl methacrylate, cyclohexyl methacrylate, etc., including the analogous acrylate or methacrylate esters.
- Copolymers of the above and other acrylic esters may be used, for example, a copolymer of methyl or ethyl acrylate and dodecyl methacrylate in conjunction with vinyl pyrrolidone.
- the polymerization should not be carried to such an extent as to form polymers which are insoluble or non-dispersible in the petroleum hydrocarbon used.
- the polymerization may be carried out by methods known to the art, such as by heating mildly in the presence of a small amount of benzoyl peroxide, but the method of polymerization is not part of this invention.
- acrylic-vinyl pyrrolidone copolymers see French Pat. No. 1,163,033.
- auxiliary chemical component is a metal deactivator for example those conveniently employed in deactivating copper, iron and other metals from hydrocarbon systems. Typical examples are those described in U.S. Pat. No. 2,282,513. Of course, one skilled in the art is aware that many other metal deactivators are known and can be employed.
- the compounds employed as metal deactivators are preferably of the type of Schiff bases and may be represented by the formulae
- a and B each represents an organic radical and preferably a hydrocarbon radical.
- a and B each preferably represents an aromatic ring or an unsaturated heterocyclic ring in which the hydroxyl radical is attached directly to a ring carbon atom ortho to the --CH ⁇ N-group.
- R represents an aliphatic radical having the two N atoms attached directly to different carbon atoms of the same open chain.
- aldehyde and polyamines employed in preparing these Schiff bases include the following:
- the ratio of the additives of this invention to the metal deactivator can vary widely depending on the particular system, the fuel, etc., employed.
- the weight ratio of additive to metal deactivator may be from about 0.1 to 20 or more, such as from about 8-15, but preferably from about 10-12.
- the weight ratio of additive to the acrylic type polymer can also vary widely from about 0.1-20 or more, such as from 8-15, but preferably from about 10-12.
- a concentrate of the additive of this invention in a solvent such as a hydrocarbon for example in concentrations of 5-75% or higher, such as from 20-60, but preferably from 40-60%.
- the additives of this invention may also be used in petroleum products to inhibit the formation of deposits on metal surfaces such as occurs in tubes, evaporators, heat exchangers, distillation and cracking equipment and the like.
Abstract
This invention relates to the hydrogenation of tetrahydropyrimidines to yield linear N-substituted diamines which can be reacted with carbonyls to form imines, which imines can be reduced to N,N'-substituted diamines as illustrated by N,N'-substituted 2,4-diamino-2-substituted pentanes. The products of this invention are useful as fuel additives.
Description
This application is a division of Ser. No. 597,564 filed July 21, 1975 and a division of Ser. No. 292,494 filed Sept. 27, 1972, now U.S. Pat. No. 4,085,104.
In Ser. No. 292,494 filed on Sept. 27, 1972, now U.S. Pat. No. 4,085,104, there is described and claimed substituted 2, 3, 4, 5-tetrahydropyrimidines (THP) ##STR1## which are prepared by the following reactions: (1) The reaction of a carbonyl compound (ketone or aldehyde) with (NH3 or NH4 OH) and a sulfur-containing catalyst.
(2) The reaction of an α,β-unsaturated ketone and a carbonyl compound and NH3 (or NH4 OH) without a catalyst.
(3) Reaction of an α,β-unsaturated ketone, a 1-amino-alcohol and NH3 (or NH4 OH) without a catalyst.
In the above formula, R1, R2, R3, R4, R5 and R6, which may be the same or different, are hydrogen or substituted group such as alkyl, aryl, cycloalkyl, alkaryl, aralkyl, heterocyclic, substituted derivatives thereof, etc. In addition R groups may be joined in a cyclic configuration which makes the THP structure a part of the substituted group.
Alkyl includes methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, escosyl, docosyl, etc., for example having about 1-25 or more carbons such as from about 1-18 carbons, but preferably about 1-12 carbons. The term "alkyl" also includes isomers of the straight chain where branching occurs.
Cycloalkyl includes cyclopentyl, cyclohexyl, etc., and derivatives thereof such as alkyl-cyclohexyl, dialkylcyclohexyl, etc.
Aryl, alkaryl and aralkyl, including phenyl, alkylphenyl, polyalkylphenyl, chlorophenyl, alkoxyphenyl, naphthyl, alkylnaphthyl, etc., benzyl, substituted benzyl, etc.
The joining of the R groups into a ring structure include those structures derived from reactants of the general formula ##STR2## such as cyclohexanone, cyclopentanone, substituted derivatives thereof such as alkyl-cyclohexanone, dialkyl-cyclohexanone.
We have now discovered that the 2,2-di-substituted derivatives of Formula I can be converted to linear diamines such as N-substituted-2,4-diamino-2-substituted pentanes by hydrogenation.
We have further discovered that such reaction occurs only with the 2,2-di-substituted tetrahydropyrimidines. Where the 2,2-di-substitution is not present, the corresponding cyclic hexahydropyrimidines are formed instead of the linear diamines.
We have further discovered that a compound of Formula II can be converted to an amine-imine by reacting with a carbonyl compound.
We have also discovered the amine-imine can be converted to the corresponding N,N'-substituted diamines by hydrogenation.
These reactions may be summarized as follows: ##STR3## or more specifically as follows: ##STR4##
Although the above reactions are illustrated with the trimethyl tetrahydropyrimidine, the methyl groups may be replaced with other groups such as for example hydrogen, higher alkyls, aryls, cycloalkyls, etc.
The hydrogenation reaction is carried out in the presence of a hydrogenation catalyst such as palladium, platinum, nickel, etc.; at a suitable temperature, for example from ambient to 200° C. or higher, but preferably 50°-150° C.; at pressures sufficient to contain hydrogen in the reaction vessel, such as about 10-2000 psi, or higher but preferably about 200-1000 psi; for a sufficient period of time for the reaction to take place such as from about 10 minutes to 24 hrs. or longer, preferably from about 1/2 hr. to 6 hrs.; in solvents which do not interfere with the catalyst, reactants, or products such as water, alcohol, hydrocarbons, esters, etc.
In addition, reduction can be effected with compositions which on reaction yield hydrogen such as metal hydrides, etc.
The linear amine resulting from hydrogenation is then reacted with a carbonyl compound of the formula ##STR5## which is either an aldehyde or a ketone.
The preparation of the imine compound is conventional. For example the reaction can be carried out by heating the amine with substantially stoichiometric amounts of the carbonyl compound under dehydrating conditions, i.e., 1:1 molar ratio, for example by the use of an azeotroping agent.
The imine compound resulting from the carbonyl reaction can be further reduced in the manner of Step 1 to yield the substituted diamine.
In the above formula, R7 and R8, which may be the same or different, are hydrogen or substituted group such as alkyl, aryl, cycloalkyl, alkaryl, aralkyl, heterocyclic, substituted derivatives thereof, etc. In addition R groups may be joined in a cyclic configuration.
Alkyl includes methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, escosyl, docosyl, etc., for example having about 1-25 or more carbons such as from about 1-18 carbons, but preferably about 1-12 carbons. The term "alkyl" also includes isomers of the straight chain where branching occurs.
Cycloalkyl includes cyclopentyl, cyclohexyl, etc., and derivatives thereof such as alkyl-cyclohexyl, dialkylcyclohexyl, etc.
Aryl, alkaryl and aralkyl include phenyl, alkylphenyl, polyalkylphenyl, chlorophenyl, alkoxyphenyl, naphthyl, alkylnaphthyl, etc., benzyl, substituted benzyl, etc.
The joining of the R groups into a ring structure include those structures derived from reactants of the general formula ##STR6## such as cyclohexanone, cyclopentanone, substituted derivatives thereof such as alkyl-cyclohexanone, dialkyl-cyclohexanone.
The following examples are presented for purposes of illustration and not of limitation.
In a 1 liter stirred autoclave was placed 95 g of 2,2-pentamethylene-4,4,6-trimethyl-2,3,4,5-tetrahydropyrimidine, 200 cc. of methanol and 6 g of 5% Pt/C catalyst. The autoclave was pressurized with 400 psi of hydrogen gas and the mixture heated for 75 minutes at 75°-80° C. while a pressure of 400-800 psi was maintained. The reaction product was removed through an internal filter leaving the catalyst behind. After removal of the solvent, there was isolated 95 g of N-cyclohexyl 2,4-diamino-2-methylpentane.
The analytical data were consistent with the assigned structure ##STR7##
Anal. calcd for C12 H26 N2 ; N, 14.14. Found: N, 13.98.
A sample of 50 g of N-cyclohexyl -2,4-diamino-2-methylpentane and 18.7 g of isobutyraldehyde in 50 cc of benzene was refluxed under azeotropical conditions for 1 hr. The benzene was removed under diminished pressure to yield 67 g of product. The product was dissolved in 200 cc of methanol and 9.6 g of sodium boronhydride was slowly added with stirring. After the reaction was completed, the solvent was removed under diminished pressure. To the resulting product was added water and the organic layer was separated. The aqueous layer was extracted with ether and the ethereal solution combined with the organic layer. After removal of the ether under diminished pressure the product was distilled under diminished pressure to yield 60 g of N-Cyclohexyl, N'-isobutyl 2,4-diamino-2-methylpentane, b0.6 =98° C.
Anal. calcd. for C16 H32 N2 ; N, 11.11. Found: N, 11.01.
The analytical data were consistent with the assigned structure ##STR8##
N-Cyclohexyl, N' isobutyl 2,4-diamino-2-methylpentane and 18.7 g of isobutyraldehyde in 50 cc of benzene was refluxed under azeotropical conditions for 1 hour. After removal of the solvent, the product was dissolved in 100 cc of methanol and placed with 2 g of a 10% Pt/C catalyst in an autoclave. The reaction was pressurized with 400 psi of hydrogen and the mixtue was heated with stirring for 3 hrs. at 75°-80° C. After removal of the catalyst by filtration, the methanol was removed under diminished pressure to yield 67 g of N-Cyclohexyl, N'-isobutyl 2,4-diamino-2-methylpentane, identical in all respects to the product isolated as described in example 2.
In a 1 liter stirred autoclave was placed 95 g of 2,2-pentamethylene 4,4,6-trimethyl 2,3,4,5-tetrahydropyrimidine, 200 cc of methanol and 6 g of 5% Pt/C catalyst. The mixture was hydrogenated with stirring for 60 minutes at 75°-80° C. and 400-800 psi of hydrogen. To the mixture was added 39 g of isobutyraldehyde and hydrogenation was continued for 3 hrs. at 75°-80° C. and 400-800 psi of hydrogen pressure. The catalyst was removed and the mixture evaporated under diminished pressure, to yield 116 g of N-cyclohexyl, N'-isobutyl 2,4-diamino-2-methylpentane, identical in all respects to the product isolated as described in example 2.
The following 2,4-diamino-2-methylpentanes were prepared, according to the methods described in examples 1-4. The results are summarized in Table I.
Table I: ______________________________________ General Structure: ##STR9## Ex. No. R.sub.1 R.sub.2 R.sub.3 R.sub.4 ______________________________________ 5 CH.sub.3 CH.sub.3 -- --* 6 CH.sub.3 CH.sub.3 H CH(CH.sub.3).sub.2 7 CH.sub.3 CH.sub.3 H CH.sub.2CH.sub.2CH.sub.3 8 CH.sub.3 CH.sub.3 H Phenyl 9 CH.sub.3 CH.sub.3 CH.sub.2CH.sub.2C(CH.sub.3)CH.sub.2CH.sub.2 10 CH.sub.3 C.sub.2 H.sub.5 -- --* 11 CH.sub.3 C.sub.2 H.sub.5 H CH(CH.sub.3).sub.2 12 (CH.sub.2).sub.5 H C.sub.2 H.sub.5 13 (CH.sub.2).sub.5 H CH.sub.2CH.sub.2CH.sub.3 14 (CH.sub.2).sub.5 (CH.sub.2).sub.5 15 (CH.sub.2).sub.5 H Phenyl 16 (CH.sub.2).sub.5 H CH(C.sub.2 H.sub.5).sub.2 17 (CH.sub.2).sub.5 H CH.sub.3 18 (CH.sub.2).sub.5 CH.sub.2CH(CH.sub.3)CH.sub.2CH.sub.2CH.sub.2 19 (CH.sub.2).sub.5 CH.sub.2CH.sub.2CH(CH.sub.3)CH.sub.2CH.sub.2 ______________________________________ ##STR10##
As is well known, fuel oils have a tendency to deteriorate in storage and form soluble colored bodies and insoluble sludge therein. This deterioration of the oil is highly undesirable in that it causes serious adverse effects on the characteristics of the oil, particularly on the ignition and burning qualities thereof. It is also a contributory factor, along with the presence of other impurities in the oil, such as rust, dirt and moisture, in causing clogging of the equipment parts, such as screens, filters, nozzles, etc., as is explained further herein. An important economical factor is also involved in the problem of oil deterioration in storage, viz., customer resistance. Thus, customers judge the quality of an oil by its color and they oftentimes refuse to purchase highly colored oils. It will be appreciated then that since fuel oils of necessity are generally subject to considerable periods of storage prior to use, the provision of a practical means for preventing the deterioration of the fuel oil during storage would be a highly desirable and important contribution to the art.
The problem of the formation of color bodies and sludge is further aggravated because fuels, such as diesel and jet fuels, are often preheated for some time before consumption, thus introducing the additional problem of thermal instability.
It has now been found that oil deterioration, with attendant formation of color and sludge in the oil, can be inhibited by employing the additives of this invention in the oil. In general, one employs a minor amount of the additive which is sufficient to inhibit oil deterioration with the attendant formation of color and sludge.
The amount of additive employed will vary depending on various factors, for example the particular oil to be stabilized, the conditions of storage, etc. The stability of an oil depends largely on the nature of the crude oil from which it is made, the type of processing involved during refining, etc., and therefore some oils will require more additive to stabilize them than others. For example, caustic-treated oil will, in general, require less additive than untreated oil of similar character. In practice, one generally employs at least about 0.0001% (1 p.p.m.), such as from about 0.0001 to 0.1% (1-1000 p.p.m.), for example about 0.0002 to 0.05% (2-500 p.p.m.), but preferably about 0.0003 to 0.03% (3-300 p.p.m.) based on weight of oil. Larger amounts, such as 1% or higher, can be employed but in general there is usually no commercial advantage in doing so.
Fuel oils in general are contemplated by the invention. The fuel oils with which this invention is especially concerned are hydrocarbon fractions having an initial boiling point of at least about 100° F. and an end point not higher than about 750° F., and boiling substantially continuously throughout their distillation range. Such fuel oils are generally known as distillate fuel oils. It will be understood, however, that this term is not restricted to straight-run distillate fractions. Thus, as is well known to those skilled in the art, the distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillates, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as acid or caustic treatment, solvent refining, clay treatment, etc.
The distillate fuel oils are characterized by their relatively low viscosities, low pour points, and the like. The principal property which characterizes the contemplated hydrocarbon fractions, however, is the distillation range. As mentioned herein, this range will lie between about 100° F. and about 750° F. Obviously, the distillation range of each individual fuel oil will cover a narrower range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.
Especially contemplated herein are Nos. 1, 2 and 3 fuel oils used in domestic heating and as diesel fuel oils, particularly those made up chiefly or entirely of cracked distillate stocks. The domestic heating oils generally conform to the specifications set forth in A.S.T.M. Specifications D396-48T. Specifications for diesel fuels are defined in A.S.T.M. Specifications D975-48T. Also contemplated herein are fuels for jet combustion engines. Typical jet fuels are defined in Military Specification MIL-F-5624B.
The following diesel fuel test is a standard test for diesel fuel stability and is regarded as a rapid screening test for discovering new systems, which can be used to stabilize petroleum distillate fuels.
In the operation of a diesel engine, a portion of the fuel sent to the fuel injection system is injected and burned; the remainder is circulated back to the fuel reservoir. The injection system is located on the engine such that the fuel being returned to the reservoir is subjected to high temperatures. Consequently, diesel fuels should exhibit good thermal stability as well as good storage stability. Since the fuels used as diesel fuel are interchangeable with furnace oils, the following procedure is used to screen the thermal stability of fuel oils in general.
The test involves exposing 50 ml. samples of fuel, containing desired quantities of fuel additives, to the test where a bath is held at 300° F. and the samples are exposed for 90 minutes.
After cooling to room temperature the exposed fuel is passed through a moderately retentive filter paper and the degree of stain on the filter paper noted. The filter paper pads are compared according to a rating of 1=best and 20 worst.
The results are presented in the following Table.
______________________________________ Product of Fuel A Fuel B Fuel C example no. 20ppm additive 20ppm additive 5ppm additive ______________________________________ no additive 18 18 11 14 4 4 4 4 3 4 2 2 4 5 2 3 3 4 2 13 4 5 3 12 4 5 4 16 5 5 3 17 4 5 3 18 5 4 5 19 7 4 4 9 8 5 9 Ratings: from 1-20 where 1 = white filter - no residue stains, and 20 = black filter - heavy residue stains ______________________________________
Although the additives of this invention are useful as fuel additives per se their performance may be enhanced by employing certain auxiliary chemical aids. Among these chemical aids are dispersants, for example acrylic polymers or copolymers which can be employed in conjunction with the cyclohexylamines.
One such auxiliary chemical component is the copolymer derived from an acrylic ester of the formula: ##STR11## and N-vinyl-2-pyrrolidone, for example a copolymer containing the following units: ##STR12## having a molecular weight for example of at least 50,000, for example 50,000-500,000, or higher, but preferably 100,000-400,000 with an optimum of 300,000-400,000 of which vinyl pyrrolidone comprises at least 1% by weight, of the polymer, for example 1-30%, but preferably 3-15% with an optimum of 5-10%; where Y is hydrogen, a lower alkyl group such as methyl, ethyl, etc., Z is an hydrocarbon group having, for example, 1-30 carbon atoms, but preferably 8 to 18 carbon atoms. These polymers are preferably acrylic or methacrylic polymers, or polymers derived from both in conjunction with vinyl pyrrolidone. The Z group on the polymer, which can be the same throughout or mixed, can be octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, etc. Lower alkyl groups can also be employed such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc., but they preferably are employed as copolymers of the higher Z groups, for example a copolymer of dodecyl methacrylate and methyl acrylate, etc. The acrylic ester units may be derived from one or more acrylic type monomers and may be fully acrylic or fully methacrylic or both acrylic and methacrylic. The polymer may be random, block, graft, etc.
Z may also be an alkylated aromatic group such as butyl phenyl, amyl phenyl, etc., or a cycloaliphatic group such as cyclohexyl. Thus, non-limiting specific examples of suitable monomeric esters are: methyl acrylate, ethyl acrylate, propyl methacrylate, amyl acrylate, lauryl acrylate, cetyl acrylate, octadecyl acrylate, amyl methacrylate, lauryl methacrylate, cetyl methacrylate, octadecyl methacrylate, amylphenyl methacrylate, cyclohexyl methacrylate, etc., including the analogous acrylate or methacrylate esters. Copolymers of the above and other acrylic esters may be used, for example, a copolymer of methyl or ethyl acrylate and dodecyl methacrylate in conjunction with vinyl pyrrolidone. However, it should be understood that this description does not preclude the presence of small amounts of unesterified groups being present in the polymer, i.e., approximately 5% or less of where Z=H.
It should be understood, of course, that when the above compounds are polymerized, the polymerization should not be carried to such an extent as to form polymers which are insoluble or non-dispersible in the petroleum hydrocarbon used. The polymerization may be carried out by methods known to the art, such as by heating mildly in the presence of a small amount of benzoyl peroxide, but the method of polymerization is not part of this invention. For examples of acrylic-vinyl pyrrolidone copolymers see French Pat. No. 1,163,033.
__________________________________________________________________________ Example of vinyl pyrrolidone-acrylic ester type resins are presented in the following table: VINYL PYRROLIDONE-ACRYLIC ESTER TYPE RESINS Vinyl pyrro- Mol lidone, per- ratio Av. mol Ex. Monomer 1 Monomer 2 Monomer 3 cent by wt. 1:2:3 weight __________________________________________________________________________ 1 Tridecyl Octadecyl methacrylate methacrylate 7.5 1:1 300,000 2 Dodecyl methacrylate 10 3 Dodecyl Butyl methacrylate acrylate 15 2:1 400,000 4 Octadecyl methacrylate 5 450,000 5 Tridecyl methacrylate 20 350,000 6 Octadecyl Methyl methacrylate methacrylate 10 3:1 500,000 7 Dodecyl Ethyl methacrylate acrylate 5 4:1 400,000 8 Cetyl Octadecyl Butyl methacrylate methacrylate methacrylate 7.5 2.1:0.5 350,000 __________________________________________________________________________
Another auxiliary chemical component is a metal deactivator for example those conveniently employed in deactivating copper, iron and other metals from hydrocarbon systems. Typical examples are those described in U.S. Pat. No. 2,282,513. Of course, one skilled in the art is aware that many other metal deactivators are known and can be employed.
The compounds employed as metal deactivators are preferably of the type of Schiff bases and may be represented by the formulae
A--CH═N--R--N═CH--B (1)
and preferably,
HO--A--CH═N--R--N═CH--B--OH (2)
wherein A and B each represents an organic radical and preferably a hydrocarbon radical. In Formula 2 A and B each preferably represents an aromatic ring or an unsaturated heterocyclic ring in which the hydroxyl radical is attached directly to a ring carbon atom ortho to the --CH═N-group. R represents an aliphatic radical having the two N atoms attached directly to different carbon atoms of the same open chain.
Typical examples of aldehyde and polyamines employed in preparing these Schiff bases include the following:
benzaldehyde
2-methylbenzaldehyde
3-methylbenzaldehyde
4-methylbenzaldehyde
2-methoxybenzaldehyde
4-methoxybenzaldehyde
2-naphthaldehyde
1-naphthaldehyde
4-phenylbenzaldehyde
Propionaldehyde
n-Butyraldehyde
Heptaldehyde
Aldol
2-hydroxybenzaldehyde
2-hydroxy-6-methylbenzaldehyde
2-hydroxy-3-methoxybenzaldehyde
2-4-dihydroxybenzaldehyde
2-6-dihydroxybenzaldehyde
2-hydroxynaphthaldehyde-1
1-hydroxynaphthaldehyde-2
Anthrol-2-aldehyde-1
2-hydroxyfluorene-aldehyde-1
4-hydroxydiphenyl-aldehyde-3
3-hydroxyphenanthrene-aldehyde-4
1-3-dihydroxy-2-4-dialdehyde-benzene
2-hydroxy-5-chlorobenzaldehyde
2-hydroxy-3-5-dibromobenzaldehyde
2-hydroxy-3-nitrobenzaldehyde
2-hydroxy-3-cyanobenzaldehyde
2-hydroxy-3-carboxybenzaldehyde
4-hydroxypyridine-aldehyde-3
4-hydroxyquinoline-aldehyde-3
7-hydroxyquinoline-aldehyde-8
ethylenediamine
1-2-propylenediamine
1-3-propylenediamine
1-6-hexamethylenediamine
1-10-decamethylenediamine
Diethylenetriamine
Triethylenetetramine
Pentaerythrityltetramine
1-2-diaminocyclohexane
Di-(b-aminoethyl)ether
Di-(b-aminoethyl)sulfide
The ratio of the additives of this invention to the metal deactivator can vary widely depending on the particular system, the fuel, etc., employed. Thus, the weight ratio of additive to metal deactivator may be from about 0.1 to 20 or more, such as from about 8-15, but preferably from about 10-12.
The weight ratio of additive to the acrylic type polymer can also vary widely from about 0.1-20 or more, such as from 8-15, but preferably from about 10-12.
For ease of handling a concentrate of the additive of this invention in a solvent such as a hydrocarbon, for example in concentrations of 5-75% or higher, such as from 20-60, but preferably from 40-60%.
The additives of this invention may also be used in petroleum products to inhibit the formation of deposits on metal surfaces such as occurs in tubes, evaporators, heat exchangers, distillation and cracking equipment and the like.
Claims (14)
1. Fuel oil containing a stabilizing amount of a stabilizer consisting of a compound of the formula ##STR13## where R5 and R6 are groups selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl, and aralkyl and R1, R2, R3, and R4 are hydrogens or a group selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl and aralkyl.
2. Fuel oil containing a stabilizing amount of a stabilizer consisting of a compound of the formula ##STR14## where R5, R6 and R7 are groups selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl and aralkyl and R1, R2, R3, R4 and R8 are hydrogens or a group selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl and aralkyl.
3. Fuel oil containing a stabilizing amount of a stabilizer consisting of a compound of the formula ##STR15## where R5, R6 and R7 are groups selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl and aralkyl and R1, R2, R3, R4 and R8 are hydrogen or a group selected from the group consisting of alkyl, aryl, cycloalkyl, alkaryl and aralkyl.
4. Fuel oil of claim 1 where R1, R3 and R4 in the compound are alkyl.
5. Fuel oil of claim 2 where R1, R3 and R4 in the compound are alkyl.
6. Fuel oil of claim 3 where R1, R3 and R4 in the compound are alkyl.
7. Fuel oil of claim 4 where R1, R3 and R4 in the compound are methyl.
8. Fuel oil of claim 5 where R1, R3 and R4 in the compound are methyl.
9. Fuel oil of claim 6 where R1, R3 and R4 in the compound are methyl.
10. Fuel oil of claim 7 where R5 and R6 in the compound are aryl, alkyl, or are joined to form a cycloalkyl group.
11. Fuel oil of claim 8 where R5 and R6 in the compound are aryl, alkyl, or are joined to form a cycloalkyl group and R7 is alkyl, aryl, or joined with R8 to form a cycloalkyl group and R8 is hydrogen or alkyl, aryl, or joined with R7 to form a cycloalkyl group.
12. Fuel oil of claim 9 where R5 and R6 in the compound are aryl, alkyl, or are joined to form a cycloalkyl group and R7 is alkyl, aryl, or joined with R8 to form a cycloalkyl group and R8 is hydrogen or alkyl, aryl, or joined with R7 to form a cycloalkyl group.
13. Fuel oil of claim 10 containing a stabilizing amount of a stabilizer consisting of at least one compound of the formula ##STR16## where R7 and R8 are joined to form a cyclic hexyl or methyl substituted cyclohexyl group.
14. Fuel oil of claim 12 containing a stabilizing amount of a stabilizer consisting of a compound of the formula ##STR17##
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/292,494 US4085104A (en) | 1972-09-27 | 1972-09-27 | Xanthates of 2,3,4,5-tetrahydropyrimidine |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US05/292,494 Division US4085104A (en) | 1972-09-27 | 1972-09-27 | Xanthates of 2,3,4,5-tetrahydropyrimidine |
US05597564 Division | 1975-07-21 |
Publications (1)
Publication Number | Publication Date |
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US4163646A true US4163646A (en) | 1979-08-07 |
Family
ID=23124917
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US05/292,494 Expired - Lifetime US4085104A (en) | 1972-09-27 | 1972-09-27 | Xanthates of 2,3,4,5-tetrahydropyrimidine |
US05/755,535 Expired - Lifetime US4163646A (en) | 1972-09-27 | 1976-12-30 | Fuel oils containing N,N-substituted diamines |
US05/806,878 Expired - Lifetime US4145545A (en) | 1972-09-27 | 1977-06-15 | Process for preparing tetrahydropyrimidines |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US05/292,494 Expired - Lifetime US4085104A (en) | 1972-09-27 | 1972-09-27 | Xanthates of 2,3,4,5-tetrahydropyrimidine |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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US05/806,878 Expired - Lifetime US4145545A (en) | 1972-09-27 | 1977-06-15 | Process for preparing tetrahydropyrimidines |
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Cited By (5)
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US4495076A (en) * | 1984-05-03 | 1985-01-22 | Mobil Oil Corporation | Lubricating oil composition containing reaction product of tetrahydropyrimidines |
US4498908A (en) * | 1984-05-03 | 1985-02-12 | Mobil Oil Corporation | Liquid fuel composition containing reaction product of tetrahydropyrimidines |
US4871374A (en) * | 1988-01-14 | 1989-10-03 | Petrolite Corporation | Fuel oils stabilized with imine-enamine condensates and method thereof |
EP0398541A2 (en) * | 1989-05-15 | 1990-11-22 | E.I. Du Pont De Nemours And Company | Aliphatic diamine for distillate fuels stabilization |
US20050215437A1 (en) * | 2004-03-26 | 2005-09-29 | Shmakova-Lindeman Olga E | Paraffin inhibitors |
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US4085104A (en) * | 1972-09-27 | 1978-04-18 | Petrolite Corporation | Xanthates of 2,3,4,5-tetrahydropyrimidine |
US4311841A (en) * | 1977-11-21 | 1982-01-19 | Petrolite Corporation | Process of preparing hexahydropyrimidines |
US4480095A (en) * | 1978-12-18 | 1984-10-30 | Petrolite Corporation | Hexahydropyrimidines and corresponding linear polyamines |
US4387074A (en) * | 1979-10-04 | 1983-06-07 | Petrolite Corporation | Polyols of tetrahydropyrimidines as corrosion inhibitors |
US4343930A (en) * | 1980-09-29 | 1982-08-10 | Petrolite Corporation | Polymerized polyols of tetrahydropyrimidines |
US4665180A (en) * | 1984-11-06 | 1987-05-12 | Petrolite Corporation | Substituted tetrahydropyrimidines and octahydrophenanthridines |
US5847035A (en) * | 1997-03-13 | 1998-12-08 | Uniroyal Chemical Company, Inc. | Substituteed tetrahydropyrimidine derivatives and their use as polymerization inhibitors for vinyl aromatic compounds |
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US4498908A (en) * | 1984-05-03 | 1985-02-12 | Mobil Oil Corporation | Liquid fuel composition containing reaction product of tetrahydropyrimidines |
US4871374A (en) * | 1988-01-14 | 1989-10-03 | Petrolite Corporation | Fuel oils stabilized with imine-enamine condensates and method thereof |
EP0398541A2 (en) * | 1989-05-15 | 1990-11-22 | E.I. Du Pont De Nemours And Company | Aliphatic diamine for distillate fuels stabilization |
EP0398541A3 (en) * | 1989-05-15 | 1991-04-17 | E.I. Du Pont De Nemours And Company | Aliphatic diamine for distillate fuels stabilization |
AU627302B2 (en) * | 1989-05-15 | 1992-08-20 | Octel America, Inc. | Aliphatic diamines for distillate fuels stabilization |
US5370712A (en) * | 1989-05-15 | 1994-12-06 | E. I. Du Pont De Nemours And Company | Aliphatic diamines for distillate fuels stabilization |
US20050215437A1 (en) * | 2004-03-26 | 2005-09-29 | Shmakova-Lindeman Olga E | Paraffin inhibitors |
US7417009B2 (en) * | 2004-03-26 | 2008-08-26 | Nalco Company | Paraffin inhibitors |
Also Published As
Publication number | Publication date |
---|---|
US4145545A (en) | 1979-03-20 |
US4085104A (en) | 1978-04-18 |
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